Occurrences of eight common-used pesticide adjuvants in ten vegetable species and implications for dietary intake in North China.

Pesticide adjuvants (PAs) are important components of pesticide products. However, limited information is available regarding their occurrences in foodstuffs. Herein, eight common-used PAs were investigated in vegetables in North China in 2014-2016. The residue levels of total PAs in vegetables from markets and farms were 500 and 661 µg/kg, respectively. The highest residues of total PAs were found in cauliflowers (average: 1.53 × 103 µg/kg, market vegetables) and spinaches (average: 3.72 × 103 µg/kg, farm vegetables), respectively. In addition, Tristyrylphenol ethoxylates (TPE) dominated the total 8 PAs concentrations in most vegetable species. Moreover, the risk assessment showed that the human health risks associated with TPE and nonylphenol (NP) exposure via vegetables for adults were acceptable, and the estimated daily intakes (EDIs) of other six PAs were in the range of <0.010-0.89 µg/kg bw/day, which were less likely to pose a threat to human health.

Effect of washing, soaking and pH in combination with ultrasound on enzymatic rancidity, phytic acid, heavy metals and coliforms of rice bran.

Simultaneous reduction in activity of fat destabilizing enzymes (lipase and lipoxygenase), contaminants heavy metals (As, Cd, Pb, and Hg), antinutrient phytic acid and hazardous coliforms in rice bran was investigated. Application of washing, soaking the washed sample at different pH values (2, 6 and 9) alone or in combination with ultrasonication were examined. While washing was beneficial, its low efficiency acquired further treatment, which was prevailed by application of acidic pH and ultrasound (28 kHz) treatments. Free fatty acids and peroxide value, as indicators of enzymes activity, implied the effectiveness of treatments with adverse impact of sonication on peroxide value. Remarkably, reduction of dominant heavy metals (As, Pb and Zn) and phytic acid were synergistically facilitated by sonication. Coliforms growth was inhibited at pH 2 even at the absence of ultrasonic treatment. Evidently, combination of acidic pH and ultrasound is a practical approach to improve rice bran stability and safety.

Impact of phosphatidylcholine and phosphatidylethanolamine on the oxidative stability of stripped peanut oil and bulk peanut oil.

Effect of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) on oxidation stability of stripped peanut oil (SPO) and bulk peanut oil (BPO) was investigated by EPR. Impact of commercial lecithin and cephalin on BPO oxidation was also studied. PC < 1000 ppm could not affect SPO oxidation but obviously accelerated oxidation above 1000 ppm. PE acted as antioxidant below 250 ppm, had no effect at 500 and 1000 ppm but behaved prooxidative properties above 2500 ppm. It suggested that there was a threshold value for PC and PE to act as prooxidant in SPO, which above the CMC yet not just at the CMC. PC (500 ppm) and PE (100-500 ppm) decreased BPO oxidation rate through reducing the formation of peroxyl and carbon-centered radicals. 250, 500 ppm PC from lecithin and 100, 250 ppm PE from cephalin possessed antioxidant abilities in BPO during Schaal oven test, demonstrating the results obtained with EPR.

Discrimination of processing grades of olive oil and other vegetable oils by monochloropropanediol esters and glycidyl esters.

In this study, the processing derived contaminants 2- and 3-monochloropropanediol (2- and 3-MCPD) esters and glycidyl esters (GEs) were analysed in 84 oil samples by GC-MS/MS for the discrimination of processing grades of olive oils as a potential authentication tool. Concentrations of 2- and 3-MCPD esters and GEs varied in the ranges 0-6 mg/kg, 0-1.5 mg/kg, and 0-1 mg/kg oil, respectively. The concentrations of the three compounds in lower grade olive oils were significantly higher (P < .001) than that in EVOO. A similar difference was observed for other refined and cold-pressed vegetable oils. The limit of fraud detection of lower grade oils in EVOO was 2% when using 3-MCPD esters, 5% for 2-MCPD esters, and 13-14% for GEs based on calculations of virtual mixtures of the current sample set. Especially the MCPD esters appear very specific and promising for the detection of lower processing grade oils in EVOO.

Emerging various environmental threats to brain and overview of surveillance system with zebrafish model.

Pathologies related to neurotoxicity represent an important percentage of the diseases that determine the global burden of diseases. Neurotoxicity may be related to the increasing levels of potentially neurotoxic agents that pollute the environment, which generates concern, since agents that affect children may increase the incidence of neurodevelopmental disorders, affecting the quality of life of future citizens. Many environmental contaminants have been detected, and many of them derive from several human activities, including the mining, agriculture, manufacturing, pharmaceutical, beverage and food industries. These problems are more acute in third world countries, where environmental regulations are lax or non-existent. An additional major emerging problem is drug contamination. Periodic monitoring should be performed to identify potential neurotoxic substances using biological tests capable of identifying the risk. In this sense the fish embryo test (FET), which is performed on zebrafish embryos, is a useful, reliable and economical alternative that can be implemented in developing countries.

Effect of temperature on thermal oxidation of palmitic acid studied by combination of EPR spin trapping technique and SPME-GC-MS/MS.

Effect of temperatures on thermal oxidation of palmitic acid was studied by the combination of EPR and GC-MS/MS. DMPO was used as the spin trap. The experimental spectrum was simulated with alkyl and alkoxyl spin adducts. Total amount of spins, a parameter to indicate radical concentrations, detected at 180°C was nearly 10 times higher than that at 175°C. Besides, total amounts of spins detected at 180°C decreased rapidly because of the reaction between radical adducts and newly formed radicals. Signal intensities of alkyl radical adducts increased rapidly from 0.405 to 4.785 from 175°C to 180°C. Besides, more palmitic acid degraded to oxidized compounds from 175°C to 180°C than that of other temperature ranges. The C-C linkages between carbons 2 to 6 were easier to be oxidized at 180°C. The results all implied that oxidation rates of palmitic acid samples increased rapidly from 175°C to 180°C.

Effect of water content on thermal oxidation of oleic acid investigated by combination of EPR spectroscopy and SPME-GC-MS/MS.

Promotion of water to the thermal oxidation of oleic acid was detected by the combination of EPR, SPME-GC-MS/MS and GC. Spin-trapping technique was used to identify and quantify the radical species formed during thermal oxidation of oleic acid by using DMPO as electron spin trap. The most abundant radical species were identified as DMPO-alkyl radical adducts. EPR intensity plateau of the samples with 5% water content was 140% higher than the samples without water. It implies oleic acid samples with high water content had high level of oxidation rates. The proportion of aldehydes of the samples with 2% water content was the maximum about 59.97%. Among the formed products, (E,E)-2,4-decadienal has genotoxic and cytotoxic effects, whose percentage was nearly twice comparing with that of 5-0% water content. This study demonstrated that higher water content in frying systems would contribute to seriously oxidation and degradation of oleic acids.

A crosslinked ß-cyclodextrin polymer used for rapid removal of a broad-spectrum of organic micropollutants from water.

Organic micropollutants in aquatic environment such as plasticizer, pesticide and pharmaceuticals, have posed a serious threat to human health and are emerging as a great challenge to humanity. Traditional water treatment techniques fail to achieve high removal efficiency for low concentration of organic micropollutants. Here we demonstrate a water-insoluble crosslinked ß-cyclodextrin (ß-CD) polymer able to remove a broad-spectrum of organic micropollutants from water by rapid adsorption. A family of ß-CD polymers (ß-CDPs) were synthesized by nucleophilic aromatic substitution of ß-CD hydroxyl groups and 4,4'-difluorodiphenylsulfone. The ß-CDPs were used to adsorb various organic micropollutants in water by static or dynamic adsorption process. It was found that more than 99% micropollutants in water were removed by flowing the feed water through the column of ß-CDPs. The results of static adsorption experiments indicated the adsorption process was fast and the adsorption capacity was very high (the maximal value was 113.0mg of bisphenol A per gram of ß-CDP). The adsorption process was fitted well with the quasi-second-order kinetics and the Langmuir isothermal adsorption model, suggesting that it is mainly a chemical adsorption of monolayer. The water-insoluble characteristic of the ß-CDPs is convenient for their separation from the treated solution after adsorption saturation for regeneration and reuse. The adsorption ability of ß-CDPs was kept nearly unchanged after five filtration-regeneration cycles.

Transcriptional kinetics of the cross-talk between the ortho-cleavage and TOL pathways of toluene biodegradation in Pseudomonas putida mt-2.

The TOL plasmid promoters are activated by toluene leading to gene expression responsible for the degradation of the environmental signal. Benzoate is formed as an intermediate, activating the BenR protein of the chromosomal ortho-cleavage pathway that up-regulates the chromosomal PbenA promoter and the TOL Pm promoter resulting in cross-talk between the two networks. Herein, the transcriptional kinetics of the PbenR and PbenA promoters in conjunction with TOL promoters was monitored by real-time PCR during toluene biodegradation of different concentrations in batch cultures. The cross-talk between the two pathways was indicated by the simultaneous maximal expression of the Pm and PbenR promoters, as well as the transcriptional activation from PbenA occurring prior to PbenR, which indicates the potential up-regulation of PbenA by the TOL XylS protein. The repressory effect of toluene on Pr was evident for concentrations higher than 0.3mM suggesting a threshold value for restoring the promoter's activity, while all the other promoters followed a specific expression pattern, regardless of the initial inducer concentration. Induction of the system with higher toluene concentrations revealed an oscillatory behaviour of Pm, the expression of which remained at high levels until the late exponential phase, demonstrating a novel function of this network.

Investigation of cutaneous penetration properties of stearic acid loaded to dendritic core-multi-shell (CMS) nanocarriers.

Dendritic core-multi shell (CMS) particles are polymer based systems consisting of a dendritic polar polyglycerol polymer core surrounded by a two-layer shell of nonpolar C18 alkyl chains and hydrophilic polyethylene glycol. Belonging to nanotransport systems (NTS) they allow the transport and storage of molecules with different chemical characters. Their amphipihilic character CMS-NTS permits good solubility in aqueous and organic solutions. We showed by multifrequency electron paramagnetic resonance (EPR) spectroscopy that spin-labeled 5-doxyl stearic acid (5DSA) can be loaded into the CMS-NTS. Furthermore, the release of 5DSA from the carrier into the stratum corneum of porcine skin was monitored ex vivo by EPR spectroscopy. Additionally, the penetration of the CMS-NTS into the skin was analyzed by fluorescence microscopy using indocarbocyanine (ICC) covalently bound to the nanocarrier. Thereby, no transport into the viable skin was observed, whereas the CMS-NTS had penetrated into the hair follicles down to a depth of 340 µm ± 82 µm. Thus, it could be shown that the combined application of fluorescence microscopy and multi-frequency EPR spectroscopy can be an efficient tool for investigating the loading of spin labeled drugs to nanocarrier systems, drug release and penetration into the skin as well as the localization of the NTS in the skin.

Evaluation of processing factors for selected organic contaminants during virgin olive oil production: Distribution of BTEXS during olives processing.

The presence of BTEXS (benzene, toluene, ethylbenzene, xylenes and styrene) in virgin olive oils can be attributed to environmental contamination, but also to biological processes during oil lipogenesis (styrene). In this work, the processing factor of BTEXS from olives to olive oil during its production was evaluated at lab-scale with an Abencor system. Benzene showed the lowest processing factor (15%), whereas toluene and xylenes showed an intermediate behavior (with 40-60% efficiency), and ethylbenzene and styrene were completely transferred (100%). In addition, an attempt to examine the contribution of potential sources to olives contamination with BTEXS was carried out for the first time. Two types of olives samples were classified according to their proximity to the contamination source (road). Although higher levels of BTEXS were found in samples close to roads, the concentrations were relatively low and do not constitute a major contribution to BTEXS usually detected in olive oil.

Radiometric assay of ghrelin hydrolase activity and 3H-ghrelin distribution into mouse tissues.

A high-throughput radiometric assay was developed to characterize enzymatic hydrolysis of ghrelin and to track the peptide's fate in vivo. The assay is based on solvent partitioning of [(3)H]-octanoic acid liberated from [(3)H]-octanoyl ghrelin during enzymatic hydrolysis. This simple and cost-effective method facilitates kinetic analysis of ghrelin hydrolase activity of native and mutated butyrylcholinesterases or carboxylesterases from multiple species. In addition, the assay's high sensitivity facilitates ready evaluation of ghrelin's pharmacokinetics and tissue distribution in mice after i.v. bolus administration of radiolabeled peptide.

Crystallization, structural relaxation and thermal degradation in Poly(L-lactide)/cellulose nanocrystal renewable nanocomposites.

In this work, crystallization, structural relaxation and thermal degradation kinetics of neat Poly(L-lactide) (PLLA) and its nanocomposites with cellulose nanocrystals (CNC) and CNC-grafted-PLLA (CNC-g-PLLA) have been studied. Although crystallinity degree of nanocomposites remains similar to that of neat homopolymer, results reveal an increase on the crystallization rate by 1.7-5 times boosted by CNC, which act as nucleating agents during the crystallization process. In addition, structural relaxation kinetics of PLLA chains has been drastically reduced by 53% and 27% with the addition of neat and grafted CNC, respectively. The thermal degradation activation energy (E) has been determined from thermogravimetric analysis in the light of Kissinger's and Ozawa-Flynn-Wall theoretical models. Results reveal a reduction on the thermal stability when in presence of CNC-g-PLLA, while raw CNC slightly increases the thermal stability of PLLA. Fourier transform infrared spectroscopy and energy dispersive X-ray spectroscopy results confirm that the presence of residual catalyst in CNC-g-PLLA plays a pivotal role in the thermal degradation behavior of nanocomposites.

Pomelo peel modified with acetic anhydride and styrene as new sorbents for removal of oil pollution.

Pomelo peel (PP), as one of the well-known agricultural wastes, is cost-effective and environmentally friendly. Based on PP, two new kinds of oil sorbents were prepared by using acetic anhydride and styrene. The structures of raw pomelo peel (RP), acetic anhydride-treated pomelo peel (AP) and styrene-treated pomelo peel (SP) were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM), contact-angle (CA) measurements. The optimum reaction conditions for preparation of AP and SP were also investigated. The resulting products exhibited better oil sorption capacity than that of RP for diesel and lubricating oil, also SP had better oil sorption capacity than AP, while the oil sorption capacities of SP for diesel and lubricating oil reached 18.91 and 26.36 g/g, respectively. Adsorption kinetics was well described by the pseudo-second-order model. The results indicated that AP and SP, especially SP could be used as the substitute for non-biodegradable oil sorption materials.

Effect of aging on volatile compounds in cooked beef.

Volatiles in the headspace of beef cooked at 180 °C were analyzed using solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS), and the effects of aging were evaluated. Seventy volatile substances including non-aromatic, homocyclic, and heterocyclic compounds were identified. A significant positive regression model for storage could be adopted for toluene, benzeneacetaldehyde, 2-formylfuran, pyrazine, 2,6-dimethylpyrazine, 2,3-dimethylpyrazine, 2-acetylthiazole, and 2-formyl-3-methylthiophene. Increases in the quantity of these compounds, with the exception of toluene, suggest the importance of the Strecker and Maillard reactions in cooked meat previously aged under vacuum conditions. As such, the aging process may lead to an increase not only in the amount of compounds related to the taste of meat, but also in the quantity of odor-active compounds. The increased quantity of toluene during storage seemed to be influenced by lipid oxidation.